Formation of CF +3 ions in photoionization of hexafluoroethane

Abstract

A detailed study of the formation of CF⁺₃ ions from C₂F₆ has been undertaken by photoelectron-photoion coincidence spectrometry. The distributions of kinetic energy released in CF⁺₃ production have been measured over a range of internal energies of the parent ion. All the CF⁺₃ ions observed are apparently formed by primary dissociation of the molecular ions; fission of the C—C bond in highly excited C₂F⁺₆ ions probably occurs before internal conversion to the ground electronic state.

The distributions of kinetic energy released in formation of CF⁺₃ from ground state C₂F⁺₆, and the rate of change of the average kinetic energy release with the ionization energy, are consistent with predictions made on the basis of statistical theories of reaction. The distributions of kinetic energy released in dissociation of highly excited C₂F⁺₆ ions are broader, and also change unexpectedly slowly with internal energy.